EP0777420B1 - Fermented sour doughs - Google Patents

Fermented sour doughs Download PDF

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Publication number
EP0777420B1
EP0777420B1 EP93915740A EP93915740A EP0777420B1 EP 0777420 B1 EP0777420 B1 EP 0777420B1 EP 93915740 A EP93915740 A EP 93915740A EP 93915740 A EP93915740 A EP 93915740A EP 0777420 B1 EP0777420 B1 EP 0777420B1
Authority
EP
European Patent Office
Prior art keywords
dough
fermented
sour
flour
water
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
EP93915740A
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German (de)
French (fr)
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EP0777420A1 (en
Inventor
Rudolf Buensow
Hans Egle
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Unilever PLC
Unilever NV
Original Assignee
Unilever PLC
Unilever NV
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Application filed by Unilever PLC, Unilever NV filed Critical Unilever PLC
Priority to EP93915740A priority Critical patent/EP0777420B1/en
Publication of EP0777420A1 publication Critical patent/EP0777420A1/en
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Classifications

    • A—HUMAN NECESSITIES
    • A21—BAKING; EDIBLE DOUGHS
    • A21D—TREATMENT OF FLOUR OR DOUGH FOR BAKING, e.g. BY ADDITION OF MATERIALS; BAKING; BAKERY PRODUCTS
    • A21D8/00—Methods for preparing or baking dough
    • A21D8/02—Methods for preparing dough; Treating dough prior to baking
    • A21D8/04—Methods for preparing dough; Treating dough prior to baking treating dough with microorganisms or enzymes
    • A21D8/045—Methods for preparing dough; Treating dough prior to baking treating dough with microorganisms or enzymes with a leaven or a composition containing acidifying bacteria

Definitions

  • Fermented sour doughs for the preparation of e.g. Rye-breads are known for quite a long time. Those known doughs, however, always contain considerable amounts of water such as about 50 wt%. It was believed that such an amount of water was necessary in order to enable the sour starter material present in those doughs to be active and to produce lactic acid and acetic acid in the dough upon fermentation.
  • fermented sour dough powders were produced by making a dough with a high water content and removing water from this dough by freeze-drying, spray-drying and/or heating.
  • freeze-drying under decreased pressure, spray-drying and/or heating of the dough was detrimental for the flavour content of the dough, as flavour components are often volatile components such as esters or acetic acid.
  • our invention concerns in the first place a fermented sour dough composition, comprising at least sour starter material (or inoculum), ground cereal kernels or grains, which will be called flour from hereon for sake of convenience and optionally bran and balance water, which dough is characterised by the presence of maximum 32 wt%, preferably 25-32 wt%, in particular 28-30 wt% of water and a pH of less than 4.2, preferably less than 4.0, in particular 3.6-4.0.
  • sour starter material or inoculum
  • ground cereal kernels or grains which will be called flour from hereon for sake of convenience and optionally bran and balance water
  • dough is characterised by the presence of maximum 32 wt%, preferably 25-32 wt%, in particular 28-30 wt% of water and a pH of less than 4.2, preferably less than 4.0, in particular 3.6-4.0.
  • the amounts of acids that are required in the dough composition depend very much on the nature of the cereal flour that is used. Suitable flours that can be applied are e.g. Rye, wheat, barley, either per se or malted or mixtures thereof. Also triticale, a grain obtained by biogenetical engineering is very good applicable.
  • the amount of acid that is produced in the sour dough depends on the kind of cereal flour that is used, preferably the titratable acidity of the dough is at least 25 (defined according to Standard-Methoden für Getreide, Mehl und Brot, 6. Erw. Auflage, Detmold 1978, p. 106-107).
  • This titratable acidity is in particular more than 30 when a whole Rye meal is used in the dough, whereas a value of more than 50, in particular more than 55 is required when a Rye-bran is applied. Interpolated data should be applied when mixtures of meal and bran are used.
  • weight ratio of lactic acid to acetic acid in sour doughs obtained after freeze-drying, spray-drying and/or heating is in general above 3.0, those ratios are in our fermented sour doughs less than 3.0.
  • the products made from the doughs according to our invention can display a shelf live of at least 6 months.
  • This long shelf live is in particular obtained when we incorporate 2-8 wt% of an organic or inorganic salt, e.g. Na-acetate, Ca-acetate, Ca-propionate, Ca-citrate, KCl and in particular NaCl in our doughs.
  • an organic or inorganic salt e.g. Na-acetate, Ca-acetate, Ca-propionate, Ca-citrate, KCl and in particular NaCl in our doughs.
  • the presence of those salts results in a lower water activity of the sour dough, of course the ratio lactic acid:acetic acid is not affected by the presence of such salts.
  • Another very convenient aspect of our invention is, that we can make a free flowing fermented sour dough with a water level of 20-25 wt%. This can be achieved by mixing of the fermented dough according to the invention with 20-38 wt% (on weight of the total mixture) of a dried flour with a water content of 1-5 wt%. Any dried flour can be used, very useful, however, is when an extruded, gelatinised cereal flour is added to our sour dough system.
  • Very good sour dough compositions which combine all desired properties, such as free-flowing, free of moulds, long shelf live and having the desired ratios latic acid:acetic acid have the following composition:
  • sour doughs according to the invention and the products made from them can also contain the usual dough or bread improver components.
  • Those components are e.g. sugar, saccharose, water-free glucose, lactose, whey-powder, emulsifiers, enzymes, yeasts etc.
  • the dough compositions can be used in order to make bakery products from them, in particular breads. Therefore, also the bakery products and breads which can be obtained after baking of compositions containing our sour doughs are also part of the invention.
  • a dried form of a leavening barm is produced that comprises viable cells of a maltose-fermenting lactobacillus and viable cells of a non-maltose fermenting Saccharomyces, whole grain flour and 5-12 wt% water.
  • Essential is that a symbiotic mixture of maltose-fermenting and non-maltose fermenting microorganisms is applied, as according to page 4, lines 30-34 of this EP in this way the composition is distinguishable from sour dough starters.
  • the drying process is very complicated and proceeds in multi-steps by the addition of flour (water content: ca. 12%) and water, followed by fermentation until a water content of about 28% is obtained (cf. example I).
  • This product is subjected to a short fermentation: 28 hrs.
  • the last drying to the required water content of 5-12% is performed by using a draft of air of about 65°C (cf. example 1).
  • the pH of the product is very low (about 3.5) in order to achieve self-preservative character.
  • Another aspect of our invention is a process for the preparation of our fermented sour doughs. This process consists of the following steps:
  • a free flowing fermented sour dough can be prepared by mixing of a fermented sour dough with a water content of 25-32 wt% and a pH ⁇ 4.2 with a food acceptable salt, such as NaCl and a dried flour with a water content of 1-5 wt% in ratios of:

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  • Life Sciences & Earth Sciences (AREA)
  • Microbiology (AREA)
  • Engineering & Computer Science (AREA)
  • Food Science & Technology (AREA)
  • Bakery Products And Manufacturing Methods Therefor (AREA)
  • General Preparation And Processing Of Foods (AREA)
  • Micro-Organisms Or Cultivation Processes Thereof (AREA)
  • Traffic Control Systems (AREA)
  • Medicines Containing Plant Substances (AREA)
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Abstract

The invention concerns fermented sour doughs, comprising starter material, ground cereal kernels or grains, balance water that contain maximum 32 wt % of water and display a pH <4.2. The titratable acidity of the doughs is at least 25, the weight ratio lactic acid: acetic acid of the doughs is <3.0. The doughs can contain salt and can be mixed with a pre-dried flour with water content 1-5 wt %. Part of the invention is also a process for the preparation of the fermented sour doughs.

Description

Fermented sour doughs for the preparation of e.g. Rye-breads are known for quite a long time. Those known doughs, however, always contain considerable amounts of water such as about 50 wt%. It was believed that such an amount of water was necessary in order to enable the sour starter material present in those doughs to be active and to produce lactic acid and acetic acid in the dough upon fermentation.
Moreover, fermented sour dough powders were produced by making a dough with a high water content and removing water from this dough by freeze-drying, spray-drying and/or heating. However, freeze-drying under decreased pressure, spray-drying and/or heating of the dough was detrimental for the flavour content of the dough, as flavour components are often volatile components such as esters or acetic acid.
We have found a solution for the problems mentioned above, whereas we further have developed a fermented sour-dough composition with a relatively low water content, wherein during fermentation the starter material was active and produced free acid, such as lactic acid and acetic acid.
Therefore, our invention concerns in the first place a fermented sour dough composition, comprising at least sour starter material (or inoculum), ground cereal kernels or grains, which will be called flour from hereon for sake of convenience and optionally bran and balance water, which dough is characterised by the presence of maximum 32 wt%, preferably 25-32 wt%, in particular 28-30 wt% of water and a pH of less than 4.2, preferably less than 4.0, in particular 3.6-4.0.
The amounts of acids that are required in the dough composition depend very much on the nature of the cereal flour that is used. Suitable flours that can be applied are e.g. Rye, wheat, barley, either per se or malted or mixtures thereof. Also triticale, a grain obtained by biogenetical engineering is very good applicable. The amount of acid that is produced in the sour dough depends on the kind of cereal flour that is used, preferably the titratable acidity of the dough is at least 25 (defined according to Standard-Methoden für Getreide, Mehl und Brot, 6. Erw. Auflage, Detmold 1978, p. 106-107). This titratable acidity is in particular more than 30 when a whole Rye meal is used in the dough, whereas a value of more than 50, in particular more than 55 is required when a Rye-bran is applied. Interpolated data should be applied when mixtures of meal and bran are used.
Whereas the weight ratio of lactic acid to acetic acid in sour doughs obtained after freeze-drying, spray-drying and/or heating is in general above 3.0, those ratios are in our fermented sour doughs less than 3.0.
As our dough compositions contain about 25-32 wt% of water it cannot be excluded that some moulds can develop in our doughs. Still the products made from the doughs according to our invention can display a shelf live of at least 6 months. This long shelf live is in particular obtained when we incorporate 2-8 wt% of an organic or inorganic salt, e.g. Na-acetate, Ca-acetate, Ca-propionate, Ca-citrate, KCl and in particular NaCl in our doughs. The presence of those salts results in a lower water activity of the sour dough, of course the ratio lactic acid:acetic acid is not affected by the presence of such salts.
Another very convenient aspect of our invention is, that we can make a free flowing fermented sour dough with a water level of 20-25 wt%. This can be achieved by mixing of the fermented dough according to the invention with 20-38 wt% (on weight of the total mixture) of a dried flour with a water content of 1-5 wt%.
Any dried flour can be used, very useful, however, is when an extruded, gelatinised cereal flour is added to our sour dough system. Very good sour dough compositions, which combine all desired properties, such as free-flowing, free of moulds, long shelf live and having the desired ratios latic acid:acetic acid have the following composition:
  • 60-70 wt% of the sour dough with less than 32 wt% of water and pH < 4.2
  • 2-8 wt% of a water activity decreasing salt
  • 22-38 wt% of the dried flour with a water content of 1-5 wt%
which dough compositions display an overall water content of 20-25 wt%, and preferably have a lactic acid to acetic acid weight ratio of less than 3.0.
Of course the sour doughs according to the invention and the products made from them can also contain the usual dough or bread improver components. Those components are e.g. sugar, saccharose, water-free glucose, lactose, whey-powder, emulsifiers, enzymes, yeasts etc.
The dough compositions can be used in order to make bakery products from them, in particular breads. Therefore, also the bakery products and breads which can be obtained after baking of compositions containing our sour doughs are also part of the invention.
According to EP 339 750 a dried form of a leavening barm is produced that comprises viable cells of a maltose-fermenting lactobacillus and viable cells of a non-maltose fermenting Saccharomyces, whole grain flour and 5-12 wt% water. Essential is that a symbiotic mixture of maltose-fermenting and non-maltose fermenting microorganisms is applied, as according to page 4, lines 30-34 of this EP in this way the composition is distinguishable from sour dough starters. The drying process is very complicated and proceeds in multi-steps by the addition of flour (water content: ca. 12%) and water, followed by fermentation until a water content of about 28% is obtained (cf. example I). This product is subjected to a short fermentation: 28 hrs. The last drying to the required water content of 5-12% is performed by using a draft of air of about 65°C (cf. example 1). The pH of the product is very low (about 3.5) in order to achieve self-preservative character.
Our product and process are different from above prior art, because in our products a sour starter material is present and not a barm, the water level is higher, the pH is higher, while we apply a pre-dried flour with a water content of 1-5 wt% instead of an air drying process. Our process, therefore, results in products with a weight ratio lactic acid:acetic acid below 3.0.
Another aspect of our invention is a process for the preparation of our fermented sour doughs. This process consists of the following steps:
stage I:
making of a dough of 60-65 wt% of water, flour and/or bran and starter material; fermenting the dough at 20-40°C during 8-24 hrs until pH is less than 4.2.
stage II:
mixing of part of dough of stage I with flour and/or bran and water until dough has water content of 58-63 wt%; fermenting this dough at 25-40°C during 2-12 hrs until pH= 3.8-4.2
stage III:
mixing of part of dough of stage II with flour and/or bran without addition of water and fermenting this dough at 20-40°C during 3-6 days until pH= 3.8-4.0.
A free flowing fermented sour dough can be prepared by mixing of a fermented sour dough with a water content of 25-32 wt% and a pH < 4.2 with a food acceptable salt, such as NaCl and a dried flour with a water content of 1-5 wt% in ratios of:
60-70
parts of sour dough of stage III
2-8
parts of the salt
22-38
parts of the dried flour
In this way a free-flowing fermented sour dough is obtained that displays a water content of 20-25 wt%.
Examples
  • I. In stage I a composition was made, containing:
    2.4 wt%
    Böcker R-starter material
    19.8 wt%
    Rye-flour
    15.0 wt%
    germ and bran of Rye
    62.8 wt%
    of water
    This composition was fermented at 30°C for 9 hrs. Its titratable acidity was 17.5 and its pH= 4.0. In stage II a composition was made of:
    12 wt%
    of product of stage I
    20.6 wt%
    of Rye-flour
    6.7 wt%
    of germ and bran of Rye
    60.7 wt%
    of water
    This mixture was fermented for 6 hrs at 30°C. Its titratable acidity was 14.5 and its pH= 4.0.In stage III a composition was made of:
    30.0 wt%
    of product of stage II
    65.8 wt%
    of Rye-flour
    4.2 wt%
    germ and bran of Rye
    This mixture was fermented for 4.5 days at 35 to 25°C (decreasing over the time period). Its titratable acidity was 30 and its pH= 3.9.
  • II To the product of stage III above, salt was added, so that a mixture of 93.7 wt% of product of stage III and 6.3 wt% of salt was obtained.
  • III A free-flowing dough powder was made by mixing of:
    67 wt%
    of product of stage III
    4.5 wt%
    NaCl
    4.5 wt%
    dehydrated dextrose
    24.0 wt%
    flour (with 3 wt% water)
    The end-product contained 20.8 wt% of water.
  • IV.1 The lactic acid and acetic acid contents and its weight ratios were measured of:
  • A: a commercial, freeze-dried product: "Molda-Roggensauer"
  • B: a freeze-dried product made from the product of stage III mentioned above
  • C: the product of example III above.
    • The results found were:
    % lactic acid % acet. acid Ratio lac acet.
    A 2.22 0.59 3.76
    B 1.83 0.59 3.10
    C 1.36 0.53 2.56
  • IV.2 A panel evaluation of the dry powders, using pair-comparison by 13 panel members and 2 presentations, revealed that the aroma intensity of the products A, B and C displayed the following profile: C > A ≈ B.

    • Claims (15)

    1. Fermented sour dough, comprising at least sour starter material, ground cereal kernels or grains and balance water characterised by a water content of the total dough of maximum 32 wt%, a pH of less than 4.2 and wherein lactic acid and acetic acid are present, in a weight ratio: lactic acid/acetic acid of less than 3.0.
    2. Fermented, sour dough, according to claim 1, wherein the water content is 25-32 wt%.
    3. Fermented sour dough, according to claim 1, wherein the pH is 3.6-4.0.
    4. Fermented sour dough, according to claim 1, wherein lactic acid and acetic acid are present in such amount that the dough displays a titratable acidity of more than 25.
    5. Fermented sour dough, according to claim 1, wherein the dough comprises whole rye meal, while the titratable acidity of the dough is more than 30.
    6. Fermented sour dough, according to claim 1, wherein the dough comprises a rye bran, while the titratable acidity of the dough is more than 50.
    7. Fermented sour dough, according to claim 1, wherein the dough contains 2-8 wt% of a food acceptable organic or inorganic salt.
    8. Fermented sour dough, wherein the dough, according to claim 1, is mixed with 20-38 wt%, on weight of the total mixture of a dried flour with a water content of 1-5 wt%, while the weight ratio lactic acid:acetic acid of the mixture is less than 3.0.
    9. Fermented sour dough, according to claim 8, wherein the dried flour is an extruded, gelatinised cereal flour.
    10. Fermented sour dough, according to claim 8, wherein 60-70 wt% of the sour dough of claim 1 are mixed with 2-8 wt% of sodium chloride and 22-38 wt% of a flour with a water content of 1-5 wt%, so that the water content of the total dough is 20-25 wt%.
    11. Fermented sour dough, according to claim 1, wherein the dough also contains one or more of the components, chosen from the group consisting of: sugar, water-free glucose, lactose, whey-powder, emulsifiers, enzymes, yeast, baking improvers and other known bread improver components.
    12. Process for the preparation of a fermented, sour dough, with the composition according to claim 1, wherein in a first stage a dough composition containing 60-65 wt% of water is made of:
      a) flour, bran or flour and bran; b) a starter material and c) water; the dough composition is fermented at 20-40°C during 8-24 hrs until the pH was dropped to less than 4.2; part of the dough of the first stage is mixed in a second stage with flour and/or bran and water until the dough displayed a water content of 58-63 wt%; the dough is fermented at 25-40°C during 2-12 hrs until the pH of the dough was 3.8-4.2 and part of the dough of stage two is mixed with flour and/or bran in a third stage, without the addition of water, whereupon the dough is fermented at 20-40°C during 3-6 days until the pH of the dough was 3.8-4.0.
    13. Process for the preparation of a free-flowing fermented sour dough, wherein a fermented sour dough with a water content of 25-32 wt% and a pH of less than 4.2 having a weight ratio lactic acid:acetic acid of less than 3.0 is mixed with a food acceptable salt and a dried flour with a water content of 1-5 wt% in ratios of 60-70 parts of sour dough to 2-8 parts of the salt to 22-38 parts of dried flour, whereby a free-flowing fermented sour dough with a water content of 20-25 wt%, having a weight ratio lactic acid:acetic acid of less than 3.0 is obtained.
    14. Bakery products, wherein the bakery products are obtained after baking of compositions, containing the sour dough of claims 1 or 7.
    15. Bread, obtained after baking of bread doughs, comprising at least partly the doughs from claims 1 or 7.
    EP93915740A 1992-07-07 1993-06-29 Fermented sour doughs Expired - Lifetime EP0777420B1 (en)

    Priority Applications (1)

    Application Number Priority Date Filing Date Title
    EP93915740A EP0777420B1 (en) 1992-07-07 1993-06-29 Fermented sour doughs

    Applications Claiming Priority (4)

    Application Number Priority Date Filing Date Title
    EP92202055 1992-07-07
    EP92202055 1992-07-07
    PCT/EP1993/001673 WO1994000994A1 (en) 1992-07-07 1993-06-29 Fermented sour doughs
    EP93915740A EP0777420B1 (en) 1992-07-07 1993-06-29 Fermented sour doughs

    Publications (2)

    Publication Number Publication Date
    EP0777420A1 EP0777420A1 (en) 1997-06-11
    EP0777420B1 true EP0777420B1 (en) 1998-08-19

    Family

    ID=8210757

    Family Applications (1)

    Application Number Title Priority Date Filing Date
    EP93915740A Expired - Lifetime EP0777420B1 (en) 1992-07-07 1993-06-29 Fermented sour doughs

    Country Status (13)

    Country Link
    US (2) US5723161A (en)
    EP (1) EP0777420B1 (en)
    JP (1) JPH07508418A (en)
    AT (1) ATE169799T1 (en)
    AU (1) AU667119B2 (en)
    CA (1) CA2139759A1 (en)
    CZ (1) CZ2695A3 (en)
    DE (1) DE69320496T2 (en)
    FI (1) FI950070A0 (en)
    HU (1) HUT69619A (en)
    PL (1) PL302680A1 (en)
    WO (1) WO1994000994A1 (en)
    ZA (1) ZA934878B (en)

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    FR2777424B1 (en) * 1998-04-15 2000-06-16 Lesaffre & Cie LAUNDRY LONG LONG CONSERVATION READY TO USE
    FR2799936B1 (en) * 1999-10-26 2002-12-06 Francis Marboutin PROCESS FOR MAKING BREAD BASED ON TRITICAL FLOUR AND BREADS THUS OBTAINED
    DE10025654A1 (en) * 2000-05-24 2001-12-06 Boehringer Backmittel Gmbh & C Storage-stable pre-dough, a process for its production and its use
    SE0103695D0 (en) * 2001-11-07 2001-11-07 Thomas Boren A novel non-antibiotic strategy against OGIP infections based on a cereal product
    ES2330101T3 (en) * 2002-11-14 2009-12-04 Puratos Naamloze Vennootschap FORMULATION TO IMPROVE THE METABOLISM OF THE TASTE OF YEAST IN SPONGE FERMENTATION SYSTEMS, OF MASS, BEER AND MASS OF MOTHER.
    WO2004080187A1 (en) * 2003-03-12 2004-09-23 Lesaffre Et Cie A sour dough, the use thereof and bakery products produced from the same
    JP2006325480A (en) * 2005-05-26 2006-12-07 Andersen Institute Of Bread & Life Co Ltd Process for producing sourdough, breads using the sourdough, pasty food, and food and drink using the same
    JP4728769B2 (en) * 2005-10-19 2011-07-20 オリヒロ株式会社 Production and utilization of sour dough containing high concentrations of γ-aminobutyric acid
    EP1854358A1 (en) * 2006-05-12 2007-11-14 Millbo S.p.a. Compositions and sour doughs for baking low glycemic index bakery products and products thereof
    IT1393389B1 (en) * 2008-10-24 2012-04-20 Bar System Europ Srl EQUIPMENT FOR ROASTING COFFEE BEANS AND EDIBLE SEEDS IN GENERAL
    DE202016101614U1 (en) * 2016-03-23 2016-05-02 Ernst Böcker Gmbh & Co. Kg Gluten-free baked goods
    EP4201211A1 (en) * 2021-12-22 2023-06-28 Silvio Umberto Lettrari Pasta sourdough cultures and methods of making same

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    DE226475C (en) *
    DE339750C (en) * 1921-08-05 Wehrlein & Co Portable electric incandescent lamp in the shape of a cigar tip
    US2023500A (en) * 1932-10-04 1935-12-10 Wogerbauer Hans Method of manufacturing a stable dry leavenous agent for baking purposes
    US2476242A (en) * 1947-05-16 1949-07-12 Ginsburg Harry Process for preparing a rye sour for baking purposes
    AT228145B (en) * 1961-11-14 1963-06-25 Vogelbusch Gmbh Process for carrying out continuous dough fermentation
    AT248985B (en) * 1964-08-10 1966-08-25 Vogelbusch Gmbh Process for preparing pre-doughs
    US4243687A (en) * 1979-01-10 1981-01-06 Leo Kline Freeze-dried natural sour dough starter
    DE3504686A1 (en) * 1985-02-12 1986-08-14 Hercules Vollkornmühlenbäckerei GmbH, 4000 Düsseldorf Process for producing a storable ready-to-use sour dough/flour mixture
    US4666719A (en) * 1985-11-05 1987-05-19 Spiller Monica A Admixture of a lactobacillus brevis and a saccharomyces dairensis for preparing leavening barm
    US4950489A (en) * 1988-04-28 1990-08-21 Alton Spiller, Inc. Preparation of dried forms of leavening barms containing an admixture of certain lactobacillus and saccharomyces species
    DE3911961A1 (en) * 1989-04-12 1990-10-18 Wilhelm Menge Stabilising effect produced by bacteria in baking leaven - by addn of salt
    GB8923841D0 (en) * 1989-10-23 1989-12-13 Unilever Plc Improvements in and relating to supported bacteria cultures and to fermentation processes

    Also Published As

    Publication number Publication date
    DE69320496T2 (en) 1999-04-15
    FI950070L (en) 1995-01-05
    EP0777420A1 (en) 1997-06-11
    PL302680A1 (en) 1994-08-22
    US5723161A (en) 1998-03-03
    DE69320496D1 (en) 1998-09-24
    HU9500048D0 (en) 1995-03-28
    US5500231A (en) 1996-03-19
    ZA934878B (en) 1995-01-09
    FI950070A7 (en) 1995-01-05
    CA2139759A1 (en) 1994-01-20
    ATE169799T1 (en) 1998-09-15
    AU667119B2 (en) 1996-03-07
    AU4561693A (en) 1994-01-31
    CZ2695A3 (en) 1995-09-13
    JPH07508418A (en) 1995-09-21
    FI950070A0 (en) 1995-01-05
    WO1994000994A1 (en) 1994-01-20
    HUT69619A (en) 1995-09-28

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